US8051647B2

US8051647B2 - Exhaust purification device of internal combustion engine

Info

Publication number: US8051647B2
Application number: US12/226,522
Authority: US
Inventors: Kenichi Tsujimoto; Shinya Hirota
Original assignee: Toyota Motor Corp
Current assignee: Toyota Motor Corp
Priority date: 2007-02-23
Filing date: 2008-02-18
Publication date: 2011-11-08
Also published as: JP2008208718A; EP2113645A4; US20090151331A1; EP2113645B1; WO2008102895A1; CN101542082B; JP4665914B2; EP2113645A1; CN101542082A

Abstract

An internal combustion engine in which a main SOx trap catalyst able to trap SOx contained in exhaust gas is arranged in an engine exhaust passage, and the exhaust passage downstream of the main SOx trap catalyst is divided into a main exhaust passage and a bypass passage bypassing the main exhaust passage. An NOx storage catalyst is arranged in the main exhaust passage, and an auxiliary SOx trap catalyst is arranged in the main exhaust passage upstream of the NOx storage catalyst. Normally, the exhaust gas is made to flow in the main exhaust passage. When regenerating the main SOx trap catalyst, the exhaust gas is made to flow through the bypass passage.

Description

TECHNICAL FIELD

The present invention relates to an exhaust purification device of an internal combustion engine.

BACKGROUND ART

Known in the art is an internal combustion engine arranging in an engine exhaust passage an NO_xstorage catalyst storing NO_xcontained in exhaust gas when the air-fuel ratio of the inflowing exhaust gas is lean and releasing the stored NO_xwhen the air-fuel ratio of the inflowing exhaust gas becomes a stoichiometric air-fuel ratio or rich. In this internal combustion engine, NO_xformed when burning fuel under a lean air-fuel ratio is stored in the NO_xstorage catalyst. On the other hand, as the NO_xstorage catalyst approaches saturation of the NO_xstorage ability, the air-fuel ratio of the exhaust gas is temporarily made rich, whereby NO_xis released from the NO_xstorage catalyst and reduced.

However, fuel and lubrication oil contain sulfur. Therefore, the exhaust gas also contains SO_x. This SO_xis stored together with the NO_xin the NO_xstorage catalyst. This SO_xis not released from the NO_xstorage catalyst by just making the exhaust gas a rich air-fuel ratio. Therefore, the amount of SO_xstored in the NO_xstorage catalyst gradually increases. As a result, the storable NO_xamount ends up gradually decreasing.

Therefore, known in the art is an internal combustion engine preventing SO_xfrom being fed into the NO_xstorage catalyst by providing an SO_xabsorbent in the engine exhaust passage upstream of the NO_xstorage catalyst (see Japanese Patent Publication (A) No. 2000-179327). In this internal combustion engine, the SO_xcontained in the exhaust gas is absorbed by the SO_xabsorbent, therefore the SO_xis prevented from flowing into the NO_xstorage catalyst. As a result, it is possible to prevent the storage of SO_xfrom causing a drop in the storage ability of the NO_x.

However, when using such an SO_xabsorbent, if the SO_xabsorbent ends up being saturated in SO_xabsorption ability, the SO_xends up flowing into the NO_xstorage catalyst. However, in this SO_xabsorbent, if raising the SO_xabsorbent in temperature and making the exhaust gas flowing into the SO_xabsorbent a rich air-fuel ratio, it is possible to make the SO_xabsorbent release the absorbed SO_xand therefore possible to regenerate the SO_xabsorbent. However, if making the SO_xabsorbent release the SO_xin this way, the released SO_xends up being stored in the NO_xstorage catalyst. Therefore, in this internal combustion engine, a bypass passage bypassing the NO_xstorage catalyst is provided and, when making the SO_xabsorbent release SO_x, the released SO_xis exhausted through the bypass passage into the atmosphere.

However, even if exhausting the SO_xreleased from the SO_xabsorbent through the bypass passage into the atmosphere at the time of regeneration of the SO_xabsorbent in this way, in actuality part of the SO_xleaks and ends up flowing into the NO_xstorage catalyst. As a result, there is a problem that the amount of SO_xstored in the NO_xstorage catalyst gradually increases.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide an exhaust purification device of an internal combustion engine able to prevent the inflow of SO_xto the NO_xstorage catalyst.

According to the present invention, there is provided an exhaust purification device of an internal combustion engine arranging in an engine exhaust passage a main SO_xtrap catalyst able to trap SO_xcontained in an exhaust gas, dividing the exhaust passage downstream of the main SO_xtrap catalyst into a main exhaust passage and a bypass passage bypassing the main exhaust passage, arranging in the main exhaust passage an NO_xstorage catalyst storage NO_xcontained in the exhaust gas when an air-fuel ratio of an inflowing exhaust gas is lean and releasing stored NO_xwhen the air-fuel ratio of the inflowing exhaust gas becomes a stoichiometric air-fuel ratio or rich, arranging in the main exhaust passage upstream of the NO_xstorage catalyst an auxiliary SO_xtrap catalyst, the exhaust gas is usually made to flow through the main exhaust passage, and the exhaust gas is made to flow through the bypass passage when the main SO_xtrap catalyst should be regenerated.

In the present invention, when making the exhaust gas flow through the bypass passage to regenerate the SO_xtrap catalyst, even if the SO_xreleased from the main SO_xtrap catalyst leaks into the main exhaust passage, this leaked SO_xis trapped by the auxiliary trap catalyst and therefore SO_xcan be prevented from flowing into the NO_xstorage catalyst.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an overview of a compression ignition type internal combustion engine,

FIG. 2 is a cross-sectional view of a surface part of a catalyst carrier of an NO_xstorage catalyst,

FIG. 3 is a cross-sectional view of a surface part of a substrate of an SO_xtrap catalyst,

FIG. 4 is a view showing the relationship between a stored SO_xamount ΣSOX and a stored SO_xamount SO(n) for control of temperature elevation,

FIG. 5 is a time chart showing the changes in the stored SO_xamount ΣSOX etc.,

FIG. 6 is a flow chart for exhaust purification control,

FIG. 7 is an overview of another embodiment of a compression ignition type internal combustion engine, and

FIG. 8 is an overview of still another embodiment of a compression ignition type internal combustion engine.

BEST MODE FOR CARRYING OUT THE INVENTION

FIG. 1 is an overview of a compression ignition type internal combustion engine.

Referring to FIG. 1, 1 indicates an engine body, 2 a combustion chamber of each cylinder, 3 an electronically controlled fuel injector injecting fuel into each

combustion chamber

2, 4 an intake manifold, and 5 an exhaust manifold. The intake manifold 4 is connected through an intake duct 6 to the outlet of a compressor 7 a of an exhaust turbocharger 7, while the inlet of the compressor 7 a is connected to an air cleaner 8. Inside the intake duct 6, a throttle valve 9 driven by the step motor is arranged. Further, around the intake duct 6, a cooling device 10 for cooling the intake air flowing through the intake duct 6 is arranged. In the embodiment shown in FIG. 1, the engine cooling water is led into the cooling device 10 where the engine cooling water is used to cool the intake air.

On the other hand, the exhaust manifold 5 is connected to the inlet of an exhaust turbine 7 b of the exhaust turbocharger 7 and the outlet of the exhaust turbine 7 b is connected to the inlet of a main SO_xtrap catalyst 11.

An exhaust pipe 12 is connected to the outlet of the main SO_xtrap catalyst 11, and an exhaust passage formed in the exhaust pipe 12 is branched into a main exhaust passage 13 and a bypass passage 14 bypassing the main exhaust passage 13. An NO_x

storage catalyst

15 is arranged in the main exhaust passage 13, and an auxiliary SO_xtrap catalyst 16 is arranged in the main exhaust passage 13 upstream of the NO_xstorage catalyst 15.

As shown in FIG. 1, a first exhaust control valve 18 which is opened or closed by an actuator 17 is arranged in the main exhaust passage 13 downstream of the NO_xstorage catalyst 15, and a second exhaust control valve 20 which is opened or closed by an actuator 19 is arranged in the bypass passage 14. As shown in FIG. 1, normally, the first exhaust control valve 18 is fully open, and the second exhaust control valve 20 is completely closed. Accordingly, normally, the exhaust gas flows within the main exhaust passage 13. On the other hand, a reducing agent feed valve 21 for feeding a reducing agent comprised of for example a hydrocarbon into the exhaust gas flowing within the exhaust manifold is attached to the exhaust manifold 5.

The exhaust manifold 5 and intake manifold 4 are connected to each other through an exhaust gas recirculation (hereinafter referred to as “EGR”) passage 22. Inside the EGR passage 22, an electronic control type EGR control valve 23 is arranged. Further, around the EGR passage 22, a cooling device 24 for cooling the EGR gas flowing through the EGR passage 22 is arranged. In the embodiment shown in FIG. 1, engine cooling water is led to the cooling device 24 where the engine cooling water cools the EGR gas. On the other hand, each fuel injector 3 is connected through a fuel tube 25 to a common rail 26. This common rail 26 is fed with fuel from an electronically controlled variable discharge fuel pump 27. The fuel fed into the common rail 26 is fed through each fuel tube 25 into the fuel injectors 3.

The electronic control unit 30 is comprised of a digital computer and is provided with a ROM (read only memory) 32, RAM (random access memory) 33, CPU (microprocessor) 34, input port 35, and output port 36 which are connected to each other by a bi-directional bus 31. As shown in FIG. 1, the accelerator pedal 40 is connected to a load sensor 41 generating an output voltage proportional to the amount of depression L of an accelerator pedal 40. The output voltage of the load sensor 40 is input through a corresponding AD converter 37 to the input port 35. Further, the input port 35 is connected to a crank angle sensor 42 generating an output pulse each time the crankshaft rotates by for example 15°. On the other hand, the output port 36 is connected through a corresponding drive circuit 38 to the fuel injectors 3, the step motor for driving the throttle valve 9, the

actuators

17, 19 for actuating the first exhaust control valve 18 and the second exhaust control valve 20, respectively, the reducing agent feed valve 21, EGR control valve 23 and the fuel pump 27.

Initially, the NO_xstorage catalyst 15 shown in FIG. 1 will be explained. This NO_xstorage catalyst 15 is comprised of a substrate on which for example a catalyst carrier comprised of alumina is carried. FIG. 2 illustrates the cross-section of the surface part of this catalyst carrier 45. As shown in FIG. 2, the catalyst carrier 45 carries a precious metal catalyst 46 diffused on the surface. Further, the catalyst carrier 45 is formed with a layer of an NO_xabsorbent 47 on its surface.

In the embodiment according to the present invention, as the precious metal catalyst 46, platinum Pt is used. As the ingredient forming the NO_xabsorbent 47, for example, at least one element selected from potassium K, sodium Na, cesium Cs, and other such alkali metals, barium Ba, calcium Ca, and other such alkali earths, lanthanum La, yttrium Y, and other rare earths is used.

If the ratio of the air and fuel (hydrocarbons) fed into the engine intake passage, combustion chamber 2, and exhaust passage upstream of the NO_xstorage catalyst 15 is called the “air-fuel ratio of the exhaust gas”, an NO_xabsorption and release action such that the NO_xabsorbent 47 absorbs the NO_xwhen the air-fuel ratio of the exhaust gas is lean and releases the absorbed NO_xwhen the oxygen concentration in the exhaust gas falls is performed.

That is, explaining this taking as an example the case of using barium Ba as the ingredient forming the NO_xabsorbent 47, when the air-fuel ratio of the exhaust gas is lean, that is, the oxygen concentration in the exhaust gas is high, the NO contained in the exhaust gas, as shown in FIG. 2, is oxidized on the platinum Pt 46 to become NO₂, next is absorbed in the NO_xabsorbent 47 and bonds with the barium oxide BaO to diffuse in the form of nitrate ions NO₃ ⁻ into the NO_xabsorbent 47. In this way, NO_xis absorbed in the NO_xabsorbent 47. So long as the oxygen concentration in the exhaust gas is high, NO₂is formed on the platinum Pt 46. So long as the NO_xabsorbent 47 is not saturated in NO_xabsorption ability, NO₂is absorbed in the NO_xabsorbent 47 and nitrate ions NO₃ ⁻ are formed.

As opposed to this, for example if the reducing agent feed valve 21 feeds the reducing agent to make the exhaust gas a rich air-fuel ratio or stoichiometric air-fuel ratio, the oxygen concentration in the exhaust gas falls, so the reaction proceeds in the reverse direction (NO₃ ⁻→NO₂), therefore the nitrate ions NO₃ ⁻ in the NO_xabsorbent 47 are released in the form of NO₂from the NO_xabsorbent 47. Next, the released NO_xis reduced by the unburned HC and CO contained in the exhaust gas.

In this way, when the air-fuel ratio of the exhaust gas is lean, that is, when burning the fuel under a lean air-fuel ratio, the NO_xin the exhaust gas is absorbed in the NO_xabsorbent 47. However, when the fuel continues to be burned under a lean air-fuel ratio, the NO_xabsorbent 47 eventually ends up becoming saturated in NO_xabsorption ability, therefore the NO_xabsorbent 47 ends up becoming unable to absorb the NO_x. Therefore, in this embodiment of the present invention, before the NO_xabsorbent 47 becomes saturated in absorption ability, the reducing agent is fed from the reducing agent feed valve 21 to make the exhaust gas temporarily rich air-fuel ratio and thereby make the NO_xabsorbent 47 release the NO_x.

Specifically speaking, in the embodiment according to the present invention, the NO_xamount NOXA stored per unit time in the NO_xstorage catalyst 15 is stored as a function of the required torque TQ and engine speed N in the form of a map shown in FIG. 4(A), and the NO_xamount ΣNOX stored in the NO_xstorage catalyst 15 is calculated by cumulatively adding this NO_xamount NOXA. In the embodiment according to the present invention, as shown in FIG. 5, every time the NO_xamount ΣNOX reaches an allowable valve NX, the air-fuel ratio A/F of the exhaust gas flowing into the NO_xstorage catalyst 15 is temporarily made rich and thereby the NO_xis released from the NO_xstorage catalyst 15.

On the other hand, the exhaust gas contains SO_x, that is, SO₂. If this SO₂flows into the NO_xstorage catalyst 15, this SO₂is oxidized on the platinum Pt 46 and becomes SO₃. Next, this SO₃is absorbed in the NO_xabsorbent 47, bonds with the barium oxide BaO, is diffused in the form of sulfate ions SO₄ ²⁻ in the NO_xabsorbent 47, and forms stable sulfate BaSO₄. However, the NO_xabsorbent 47 has a strong basicity, so this sulfate BaSO₄is stable and hard to break down. If just making the exhaust gas rich air-fuel ratio, the sulfate BaSO₄remains as is without breaking down. Therefore, in the NO_xabsorbent 47, the sulfate BaSO₄increases along with the elapse of time, therefore the NO_xamount which the NO_xabsorbent 47 can absorb falls along with the elapse of time.

Therefore, in an embodiment of the present invention, the main SO_xtrap catalyst 11 is arranged upstream of the NO_xstorage catalyst 15 to trap the SO_xcontained in the exhaust gas by this main SO_xtrap catalyst 11 and thereby prevent SO_xfrom flowing into the NO_xstorage catalyst 15. Next this main SO_xtrap catalyst 11 will be explained.

This main SO_xtrap catalyst 11 is comprised of for example a monolithic catalyst having a honeycomb construction and has a plurality of exhaust gas flow passages extending straight in the axial direction of the main SO_xtrap catalyst 11.

FIG. 3 illustrates the cross-section of the surface part of a substrate 50 of this main SO_xtrap catalyst 11. As shown in FIG. 3, the substrate 50 is formed with a coat layer 51 on its surface. This coat layer 51 carries a precious metal catalyst 52 diffused on its surface.

In the embodiment according to the present invention, as the precious metal catalyst 52, platinum is used. As the ingredient forming the coat layer 51, for example, at least one element selected from potassium K, sodium Na, cesium Cs, and other such alkali metals, barium Ba, calcium Ca, and other such alkali earths, lanthanum La, yttrium Y, and other rare earths is used. That is, the coat layer 51 of the main SO_xtrap catalyst 11 exhibits a strong basicity.

Now, the SO_xcontained in the exhaust gas, that is, SO₂, is oxidized on the platinum Pt 52 as shown in FIG. 3, then is trapped in the coat layer 51. That is, the SO₂diffuses in the form of sulfate ions SO₄ ²⁻ in the coat layer 51 to form a sulfate. Note that as explained above, the coat layer 51 exhibits a strong basicity. Therefore, as shown in FIG. 3, part of the SO₂contained in the exhaust gas is directly trapped in the coat layer 51.

In FIG. 3, the shading in the coat layer 51 shows the concentration of the trapped SO_x. As will be understood from FIG. 3, the SO_xconcentration in the coat layer 51 is highest near the surface of the coat layer 51. The further in, the lower it becomes. If the SO_xconcentration near the surface of the coat layer 51 increases, the surface of the coat layer 66 weakens in basicity and the SO_xtrap ability weakens. Here, if the ratio of the amount of the SO_xtrapped in the main SO_xtrap catalyst 11 to the amount of the SO_xin the exhaust gas is called the “SO_xtrap rate”, if the basicity of the surface of the coat layer 51 is weakened, the SO_xtrap rate falls along with that. In the embodiment according to the present invention, when the SO_xtrap rate falls below a predetermined rate, a temperature raising control for raising the temperature of the main SO_xtrap catalyst 11 under a lean or rich exhaust gas air-fuel ratio is performed and thereby the SO_xtrap rate is restored.

Namely, if raising the temperature of the main SO_xtrap catalyst 11 when the air-fuel ratio of the exhaust gas is lean, the SO_xpresent concentrated near the surface of the coat layer 51 diffuses toward the deep part of the coat layer 51 so that the concentration becomes uniform. That is, the nitrates formed in the coat layer 51 change from an unstable state where they concentrate near the surface of the coat layer 51 to the stable state where they are diffused evenly across the entire inside of the coat layer 51. If the SO_xpresent near the surface of the coat layer 51 diffuses toward the deep part of the coat layer 51, the SO_xconcentration near the surface of the coat layer 51 falls. Therefore, when the temperature raising control of the main SO_xtrap catalyst 11 has ended, the SO_xtrap rate is restored.

If making the temperature of the main SO_xtrap catalyst 11 about 450° C. when performing the temperature raising control of the main SO_xtrap catalyst 11, it is possible to make the SOX present near the surface of the coat layer 51 diffuse in the coat layer 51. If raising the temperature of the main SO_xtrap catalyst 51 to 600° C. or so, the SO_xconcentration in the coat layer 51 can be made considerably even. Therefore, at the time of temperature raising control of the main SO_xtrap catalyst 11, it is preferable to raise the temperature of the main SO_xtrap catalyst 11 to 600° C. or so under a lean air-fuel ratio of the exhaust gas.

Next, an embodiment of the temperature raising control of the main SO_xtrap catalyst 11 will be specifically explained.

In this embodiment, the SO_xamount trapped by the main SO_xtrap catalyst 11 is estimated. When the SO_xamount trapped by the main SO_xtrap catalyst 11 exceeds a predetermined amount, it is judged that the SO_xtrap rate has fallen below the predetermined rate. At this time, to restore the SO_xtrap rate, the temperature raising control of raising the temperature of the main SO_xtrap catalyst 11 under a lean air-fuel ratio of the exhaust gas is performed.

That is, fuel contains sulfur in a certain ratio. Therefore, the amount of SO_xcontained in the exhaust gas, that is, the amount of SO_xtrapped by the main SO_xtrap catalyst 11, is proportional to the amount of fuel injection. The amount of fuel injection is a function of the required torque and engine speed. Therefore, the amount of SO_xtrapped by the main SO_xtrap catalyst 11 becomes a function of the required torque and engine speed. In this embodiment according to the present invention, the SO_xamount SOXA trapped per unit time in the main SO_xtrap catalyst 11 is stored as a function of the required torque TQ and engine speed N in the form of a map shown in FIG. 4(B) in advance in the ROM 32.

Further, in this embodiment, as shown in FIG. 4(C), the relationship of the SO_xamount ΣSOX and the predetermined SO_xamount SO(n) when the main SO_xtrap catalyst 11 should be raised in temperature is stored in advance. When the SO_xamount ΣSOX exceeds a predetermined SO(n) (n=1, 2, 3, . . . ), the temperature raising treatment is performed to raise the temperature of the main SO_xtrap catalyst 11. Note that in FIG. 4(C), n indicates what number time the temperature raising treatment is. As will be understood from FIG. 4(C), as the number of times n of temperature raising treatment for restoring the SO_xtrap rate increases, the predetermined amount SO(n) is increased. The rate of increase of this predetermined amount SO(n) is reduced the greater the number of times n of treatment. That is, the rate of increase of SO(3) with respect to SO(2) is reduced from the rate of increase of SO(2) with respect to SO(1).

That is, as shown in FIG. 5, in this embodiment, when the SO_xamount ΣSOX reaches SO(n), the temperature T of the main SO_xtrap catalyst 11 is raised to 600° C. or so and is maintained at 600° C. or so under a lean air-fuel ratio of the exhaust gas. Note that in this embodiment, at the time of temperature raising control, hydrocarbons if fed from the hydrocarbon supply valve 21 and the temperature of the main SO_xtrap catalyst 11 is raised by the heat of oxidation reaction of the hydrocarbons.

On the other hand, if making the exhaust gas a rich air-fuel ratio when raising the temperature of the main SO_xtrap catalyst 11 in this way, the main SO_xtrap catalyst 11 ends up releasing SO_x. Therefore, in this embodiment, at the time of temperature raising control, the exhaust gas is maintained at a lean air-fuel ratio. However, when the SO_xconcentration near the surface of the coat layer 51 becomes high, even if the exhaust gas is maintained at a lean air-fuel ratio, the main SO_xtrap catalyst 11 ends up releasing SO_xwhen the main SO_xtrap catalyst 11 is raised in temperature. Therefore, at this time, to prevent the SO_xfrom flowing into the NO_xstorage catalyst 15, the first exhaust control valve 18 is closed and the second exhaust control valve 20 is opened. That is, as shown in FIG. 5, at the time of the temperature raising control of the main SO_xtrap catalyst 11, the exhaust passage is switched from the main exhaust passage 13 to the bypass passage 14.

However, even if the first exhaust control valve 18 is closed, the exhaust gas actually passes around the first exhaust control valve 18 and leaks out. Therefore, even if the first exhaust control valve 18 is closed and the second exhaust control valve 20 is opened, while a small amount, exhaust gas flows into the main exhaust passage 13, therefore the SO_xexhausted from the main SO_xtrap catalyst 11 flows into the NO_xstorage catalyst 15.

Therefore, in the present invention, to prevent the SO_xfrom flowing into the NO_xstorage catalyst 15, as shown in FIG. 1, an auxiliary SO_xtrap catalyst 16 is arranged inside the main exhaust passage 13 upstream of the NO_xstorage catalyst 15. This auxiliary SO_xtrap catalyst 16 has a structure similar to the main SO_xtrap catalyst 11. In this auxiliary SO_xtrap catalyst 16, as shown in FIG. 3, a coat layer 51 is formed on the surface of the catalyst carrier 50. A precious metal catalyst 52 is carried and dispersed on the surface of this coat layer 51.

Furthermore, even with this auxiliary SO_xtrap catalyst 16, platinum is used as the precious metal catalyst 52, and, as the ingredient forming the coat layer 51, at least one element selected from for example potassium K, sodium Na, cesium Cs, or another such alkali metal, barium Ba, calcium Ca, or another such alkali earth, lanthanum La, yttrium Y, or another such rare earth is used.

Note that this auxiliary SO_xtrap catalyst 16 is never regenerated like the main SO_xtrap catalyst 11. This auxiliary SO_xtrap catalyst 16 is made to perform an SO_xtrapping action permanently. Therefore, in this embodiment according to the present invention, the basicity of the coat layer 51 of the auxiliary SO_xtrap catalyst 16 is made stronger than the basicity of the coat layer 51 of the main SO_xtrap catalyst 11. Therefore, the auxiliary SO_xtrap catalyst 16 is made higher in SO_xholding capacity compared with the main SO_xtrap catalyst 11.

Next, an exhaust purification control routine will be explained with reference to FIG. 6.

Referring to FIG. 6, first, at step 60, the NO_xamount NOXA stored in the NO_xstorage catalyst 15 per unit time is calculated from the map shown in FIG. 4(A). Next, at step 61, this NOXA is added to the NO_xamount ΣNOX stored in the NOX storage catalyst 15. Next, at step 62, it is judged whether the stored NO_xamount ΣNOX exceeds the allowable value NX. When ΣNOX>NX, the routine proceeds to step 63 where the rich processing of switching the air-fuel ratio of the exhaust gas flowing into the NO_xstorage catalyst 15 temporarily from lean to rich by the reducing agent supplied from the reducing agent supply valve 21 is performed and the ΣNOX is cleared.

At this time, as shown in FIG. 1, the first exhaust control valve 18 is opened, and the second exhaust control valve 20 is closed. That is, the exhaust gas flows through the main exhaust passage 13. Further, as will be understood from FIG. 5, at this time, the main SO_xtrap catalyst 11 is not raised in temperature, so usually SO_xis never exhausted from the main SO_xtrap catalyst 11, but if at this time the main SO_xtrap catalyst 11 were to release SO_x, this SO_xwould be trapped in the auxiliary SO_xtrap catalyst 11. Therefore, at the time of NO_xrelease control, the SO_xnever flows into the NO_xstorage catalyst 15.

Next, at step 64, the SO_xamount SOXA stored in the main SO_xtrap catalyst 11 per unit time is calculated from the map shown in FIG. 4(B). Next, at step 65, this SOXA is added to the SO_xamount ΣSOX trapped by the main SO_xtrap catalyst 11. Next, at step 66, it is judged if the SO_xamount ΣEOX reaches the predetermined amount SO(n) (n=1, 2, 3, . . . ) shown in FIG. 4(C). When the SO_xamount ΣSOX reaches the predetermined amount SO(n), the routine proceeds to step 67 where, as shown in FIG. 5, the exhaust passage is switched from the main exhaust passage 13 to the bypass passage 14. Next, at step 68, the regeneration control such that the temperature of the main SO_xtrap catalyst 11 is maintained at 600° C. or so under a lean air-fuel ratio of the exhaust gas is performed. When the regeneration treatment ends, the ΣSOX is clear, and the exhaust passage is again switched to the main exhaust passage 13.

Further, when regenerating the main SO_xtrap catalyst 11, it is also possible to make the exhaust gas a rich air-fuel ratio as shown by the broken line in FIG. 5. At this time, as explained above, the main SO_xtrap catalyst 11 releases a large amount of SO_x. This released large amount of SO_xis fed into the bypass passage 14. At this time as well, when SO_xflows into the main exhaust passage 13, this inflowing SO_xis trapped at the auxiliary SO_xtrap catalyst 16.

FIG. 7 shows another embodiment of a compression ignition type internal combustion engine. In this embodiment, the main SO_xtrap catalyst 70 is comprised of a serially arranged SO_x

trap catalyst

71 and particulate filter 72. In this embodiment, when the particulate filter 72 is raised in temperature under a lean air-fuel ratio of the exhaust gas so as to regenerate the particulate filter 72, the SO_xtrap catalyst 71 is also regenerated. Note that the NO_xstorage catalyst can also be carried on the particulate filter 72.

FIG. 8 shows still another embodiment of a compression ignition type internal combustion engine. In this embodiment, the main SO_xtrap catalyst 73 is comprised of an NO_xstorage catalyst. When regenerating this NO_xstorage catalyst 73, the temperature of the NO_xstorage catalyst 73 is raised up to 600° C. or more and the exhaust gas flowing into the NO_xstorage catalyst 73 is made a rich air-fuel ratio. At this time, SO_xis released from the NO_xstoring catalyst 73.

Claims

1. An exhaust purification device of an internal combustion engine comprising:

a main SO_xtrap catalyst arranged in an engine exhaust passage, for trapping SO_xcontained in an exhaust gas, dividing the exhaust passage downstream of the main SO_xtrap catalyst into a main exhaust passage and a bypass passage bypassing the main exhaust passage;

an NO_xstorage catalyst arranged in the main exhaust passage for storing NO_xcontained in the exhaust gas when an air-fuel ratio of an inflowing exhaust gas is lean and releasing stored NO_xwhen the air-fuel ratio of the inflowing exhaust gas becomes a stoichiometric air-fuel ratio or rich; and

an auxiliary SO_xtrap catalyst arranged in the main exhaust passage upstream of the NO_xstorage catalyst, the exhaust gas is made to flow through the main exhaust passage, and the exhaust gas is made to flow through the bypass passage when the main SO_xtrap catalyst is regenerated, wherein

the main SO_xtrap catalyst has a property that when the main SO_xtrap catalyst rises in temperature under a lean air-fuel ratio of the exhaust gas, the trapped SO_xgradually diffuses inside the main NO_xtrap catalyst and has a property that when the air-fuel ratio of the exhaust gas flowing into the main SO_xtrap catalyst becomes rich, if the temperature of the main SO_xtrap catalyst is higher an SO_xrelease temperature, the trapped SO_xis released, and when the SO_xtrap rate by the main SO_xtrap catalyst falls below a predetermined rate, a regeneration action of the main SO_xtrap catalyst is performed.

2. An exhaust purification device of an internal combustion engine as set forth in claim 1, wherein the auxiliary SO_xtrap catalyst has a higher SO_xholding ability than the main SO_xtrap catalyst.

3. An exhaust purification device of an internal combustion engine as set forth in claim 1, wherein the auxiliary SO_xtrap catalyst comprises a coat layer formed on a substrate and a precious metal catalyst held on the coat layer and the coat layer has an alkali metal, alkali earth metal, or rare earth metal dispersed in the coat layer.

4. An exhaust purification device of an internal combustion engine as set forth in claim 1, wherein when regenerating the main SO_xtrap catalyst, the main SO_xtrap catalyst is raised in temperature in a state maintaining the air-fuel ratio of the exhaust gas flowing into the main SO_xtrap catalyst lean without allowing it to become rich.

5. An exhaust purification device of an internal combustion engine as set forth in claim 1, wherein when regenerating the main SO_xtrap catalyst, the air-fuel ratio of the exhaust gas flowing into the main SO_xtrap catalyst is made rich.

6. An exhaust purification device of an internal combustion engine as set forth in claim 1, wherein the main SO_xtrap catalyst comprises a serially arranged SO_xtrap catalyst and particulate filter.

7. An exhaust purification device of an internal combustion engine as set forth in claim 1, wherein the main SO_xtrap catalyst comprises an NO_xstorage catalyst.